N-alkylation of aromatic amines

ABSTRACT

X IS AN INTEGER FROM 0 TO 23 INCLUSIVE; Y IS AN INTEGER FROM 0 TO 23 INCLUSIVE; AND X+Y IS 0 TO 23.   -COOH OR -COO-LOWERALKYL   Y IS -CH=N-OR -CH2-NH-WHEREIN THE NITROGEN ATOM IS DIRECTLY BONDED TO R4; R4 IS AN AROMATIC RADICAL; R5 IS -H, -CH3, -CH, -OH, -CHO, -NH2   WHEREIN:   C2H5-(CH2)X-CH(-Y-R4)-CH2-(CH2)Y-R5   AN N-ALKYLATED AROMATIC AMINE OF THE FORMULA:   A METHOD FOR PRODUCING N-ALKYLATED AROMATIC AMINES COMPRISING COREACTING CARBON MONOXIDE, HYDROGEN, AN AROMATIC AMINE, AND AN OLEFINIC COMPOUND AT PRESSURES ABOVE 200 P.S.I. IN THE PRESENCE OF A CATALYST WHICH IS THE REACTION PRODUCT OF: (A) A SALT SELECTED FROM THE GROUP CONSISTING OF RHODIUM HALIDES, RUTENIUM HALIDES, AND COBALT CARBONYLS, WITH (B) A COMPLEXING AGENT SELECTED FROM T HE GROUP CONSISTING OF TRIHYDROCARBYL PHOSPHINE, TRIHYDROCARBYL ARSINE, AND TRIHYDROCARBYL STIBINE.

United States Patent 3,600,413 Patented Aug. 17, 11971.

3,600,413 N-ALKYLATION F AROMATIC AMINIES Robert A. Grimm, Lakeville,Minn, assignor to Ashland Gil & Refining Company, Houston, Tex. NoDrawing. Filed May 16, 1968, Ser. No, 729,563 Int. Cl. C09f 7/00; (107s121/52, 101/78, 87/28, 29/02 US. Cl. 260404 8 Claims ABSTRACT OF THEDISCLOSURE A method for producing N-alkylated aromatic amines comprisingcoreacting carbon monoxide, hydrogen, an aromatic amine, and an olefiniccompound at pressures above 200 p.s.i. in the presence of a catalystwhich is the reaction product of:

(A) a salt selected from the group consisting of rhodium halides,ruthenium halides, and cobalt carbonyls, with (B) a complexing agentselected from the group consisting of trihydrocarbyl phosphine,trihydrocarbyl arsine, and trihydrocarbyl stibine.

An N-alkylated aromatic amine of the formula:

i. wherein:

Y is CH=N or CH NH wherein the nitrogen atom is directly bonded to R Ris an aromatic radical; R is -H, CH CH, OH, -CHO, NH

0 fl-OH, orflO-(lower alkyl):

x is an integer from O to 23 inclusive; y is an integer from 0 to '23inclusive; and x+y is 0 to 23.

This invention relates to the synthesis of certain classes ofN-alkylated aromatic amines. These classes are anils, also known asSchiffs bases; N-alkylated aromatic secondary amines; and N-alkylatedaromatic tertiary amines.

According to the present invention, there is provided a method forproducing N-alkylated aromatic amines, comprising coreacting carbonmonoxide, hydrogen, an aromatic amine, and an olefinic compound atpressures above 200 p.s.i. in the presence of a catalyst which is thereaction product of:

(A) a salt selected from the group consisting of rhodium halides,ruthenium halides, and cobalt carbonyls, with (B) a complexing agentselected from the group consisting of trihydrocarbyl phosphine,trihydrocarbyl arsine, and trihydrocarbyl stibine.

wherein R is a hydrocarbyl radical, and is preferably phenyl or loweralkyl, and X is arsenic or antimony, or, preferably, phosphorus. Themost preferred single catalyst is rhodium trichloridetris(tripheny1phosphine) because of its ease of formation and the highyield of N- alkylated aromatic amine. The catalysts can be employed inany amount sufficient to catalyze the reactant and are generally presentin an amount equal to 0.1 to 5.0, and preferably 0.2 to- 0.4 weightpercent of catalyst, based on the weight of the olefinic material.

A broad class of amines can be employed in the present invention, butthe preferred amines are aromatic amines having a dissociation constant,pK, measured in aqueous solution of from 8.5 to 11.5, and preferably 9to 10. Aromatic amines with dissociation constants outside these rangescan be employed, but the reaction rate is adversely affected. Apreferred class of aromatic amines are those of Formula II:

wherein R is halogen, lower alkyl, or lower alkoxy, and a is an integerfrom 0 to 3 inclusive. Examples of suitable aromatic amines include,among others, aniline; o-, m-, and p-anisidine; mand p chloroaniline;o-, mand p-toluidine; 2,3- 2,5-, and 2,6-xyl1idine;2-bromo-4,6-dichloroaniline; l-amino naphthalene; 1-amino-4-bromonaphthalene; 1amino-2,4-dibromonaphthalene; .l-amino-4-fluoronaphthalene; l-amino-3-methyl-naphthalene; 1,6-diaminonaphthalene; p-phenylene diamine; and N-phenyl-p-phenylenediamine. Aniline is the most preferred aromatic amine because of cost,availability, and reactivity. Nonaromatic amines, such as ammonia,methylamine, and diethylamine, are unsuitable because they inhibit thereaction of the aromatic amine and do not thelmseves undergo reaction.

A broad class of olefinic compounds can be employed in the presentinvention, although certain classes are preferred. The olefinic compoundcan have one or more, but preferably has one ethylenically unsaturateddouble bond which can be internal or terminal. In general, olefiniccompounds having only one ethylenically unsaturated double bond reactfaster than compounds having a plurality of such double bonds, and, ingeneral, compounds in which the double bond is terminal, i.e. thosehaving a vinyl group of the formula CH C react faster than compounds inwhich the double bond is internal. Examples of suitable classes ofolefinic compounds include ethylenically unsaturated fatty acids,ethylenically unsaturated fatty nitriles, alpha-olefins, dienes, vinylmonomers, and acrylic monomers. A class of preferred olefinic compoundsare those of Formula III:

( C H R wherein n is an integer from 2 to 27 inclusive; m equals Zn or2n-1 or 2n2; and R is H, OH, CN, or

wherein p is an integer from 1 to 27 inclusive.

The preferred olefinic compounds of Formula III are the alpha-olefins ofFormula IV:

wherein n is an integer from 4 to 25 inclusive.

Yet another class of olefinic compounds are the cyclic olefins ofFormula V:

wherein n is an integer from 2 to 8 inclusive, and m equals 2n-2 or2n-3. Examples of suitable olefinic compounds include, among others,a-olefins such as l-hexene, l-octene, l-hexadecen, l-docosene, andl,l-dimethylethylene; substituted a-olefins such as ethyl undecylenate;internal olefins such as 2-hexene, 3-octene, 4-octene, mixedhexadecenes, 3-methyloctene-3, and cyclohexene; substituted internalolefins such as methyl oleate, ethyl oleate, oleonitrile, methylpalmitoleate, and oleyl alcohol; dienes such as 1,5-cyclooctadiene,ethyl linoleate, linoleic acid, and linoleyl alcohol; conjugateddiolefins such as 1,3-butadiene, acrylonitrile, ethyl methyl acrylate,methyl acrylate; aromatic olefins such as stilbene and styrene; andnaturally occurring triglycerides of ethylenically unsaturated fattyacids such as tallow, soybean oil, coconut oil, linseed oil, cottonseedoil, tung oil, and oiticica oil.

The process of the present invention is practiced by combining thereactants in a suitable reactor at pressures of 200 to 2000, andpreferably 1000 to 1500 p.s.i.g., until the reaction is complete asindicated by an increase in pressure when additional carbon monoxide andhydrogen are added. The N-alkylated aromatic amines produced by theprocess of the present invention will be N-alkylated aromatic secondaryamines or N-alkylated aromatic tertiary amines or anils, depending uponreactants and reaction conditions. At temperatures of 50 to 125 C., thereaction proceeds according to Equation 1 to give a product which isalmost exclusively that anil, whereas at temperatures of 150 to 200 C.,the reaction proceeds according to Equation 2 or 3 to give a productwhich is almost exclusively the above-described secondary or tertiaryamines. Thus, the anils are produced at temperatures of about 50 to 150C., and the N-alkylated aromatic secondary and tertiary amines areproduced at temperatures of about 125 to 200 C. The above-describedtertiary amines usually result when the olefinic compound has terminalunsaturation and is present in a molar ratio of olefiniccompoundzaromatic amine of greater than 1:1 as shown in Equation 2,whereas the above-described secondary amines usually result when theolefinic compound has internal unsaturation according to Equation 3.

(Equation 1) C H BANHZ CH=CH CH-CH2- H2O H II N (aromatic (olefinicamine) compound) R (anil) (Equation 2) 200 4H2 BANE; 2CH =CH (aromatic(oz-olefin) amine) OH;OH2CH CHzGHgCH2 (N-alkylated aromatic tertiaryamine) The reaction can be conducted in the absence of solvents.However, common solvents such as ethanol, methanol, and benzene do notadversely affect the reaction. Although the reactants are preferablycombined in the stoichiometric ratios shown in Equations 1, 2, and 3, awide variety of ratios can be employed. The molar ratios of aromaticamines to olefinic compound is 10:1 to 1:10, and preferably 1:1 to 4:1.Greater amounts of excess aromatic amine can be employed but are simplyrecovered unreacted. The molar ratio of hydrogen to carbon monoxide canbe from 1:2 to 10:1, but no advantage is achieved by departing from thestoichiometric ratio of 2:1 when producing N-alkylated aromatic amines;or 1:1 when producing anils. Partial pressuresof carbon monoxide inexcess of 0.6 of the total reaction pressure should be avoided, sincethey have been found to inhibit the reaction. If such a partial pressureaccidentally occurs, the reaction can be restarted by venting thereactor to reduce the partial pressure of carbon monoxide and by addinghydrogen to re-establish the desired hydrogenzcarbon monoxide ratio.

According to another aspect of the present invention, there are providednovel fatty N-alkylated aromatic amines of Formula VI:

0,115 \om/ I wherein Y is -CH=N- or CH NH- wherein the nitrogen atom isdirectly bonded to R R is an aromatic radical of 6 to 20 carbon atoms,but is preferably phenyl or naphthyl; R is H, CH -CN, -OH, -CHO, NH

' oxidation of the fatty alcohols. The fatty amines of Formula VI can beproduced by hydrogenation of the fatty nitriles.

All of the compounds of the present invention, as well as the saturatedanalogs, can be quaternized with hydrocarbyl halides such as methylchloride or benzyl chloride, to produce quaternary ammonium compoundswhich when applied in the form of emulsions to fabrics such as cottonwill render the fabric softer and/ or bacteriostatic and/ or antistatic.The acid salts of the monoand dialkylanilines, such as thehydrochlorides, hydrobromides, and acid sulfates, when applied as anemulsion or solution to wood surfaces, inhibit attack by rodents. Theseacid salts, in particular the hydrochlorides, hydrobromides, andphosphates, are also useful as components of gasoline wherein theyprevent or inhibit carburetor icing. For this application, compounds ofFormula VI, wherein x+y is at least 6, are desirable because of theirincreased solubility in gasoline. The dialkyl and monoalkylanilines; theacid salts of N-phenylaminomethylated oleic acid, ethyl oleate,triglycerides, and oleylnitrile are also suitable for this application.The acids and esters of Formula VI, wherein Y is CH NH, are useful astextile modifiers or can be employed to modify known wash and wearresins. The apparent reaction by which modification occurs isesterification of the acid or ester with the resin. N-phenylaminomethylstearyl amine, when reacted with a diisocyanate such as General MillsDDI, a C aliphatic diisocyanate, gives a composition that can be appliedto substrates as a protective or decorative coating. These compositionscure to a tough, clear, flexible polymeric film. Similarly, theN-cyclohexylaminostearyl amine is useful in polyureas, or can be reactedwith diacids to give novel polyamides.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise indicated.These nonlimiting examples are illustrative of certain embodimentsdesigned to teach those skilled in the art how to practice the inventionand to represent the best mode presently known for carrying out theinvention. In these examples TAN means Total Amine Nitrogen, TLC meansthin layer chromatography, and IR means infra-red. In these examples, zis employed to designate the number of the carbon atom of the fattyradical to which the aromatic amino methylene radical is attached. Thearomatic amino methylene radical can attach to either of the carbonatoms of the original double bond, and the double bond can be located ina number of places in the fatty chain, as is well-known in the art.Thus, 2 can be any integer from 6 to 14 inclusive. NMR means nuclearmagnetic resonance.

EXAMPLE 1 This example illustrates the synthesis of a rhodium catalyst,termed Catalyst A, useful in the present invention.

Triphenyl phosphine (15 g.) is dissolved in a hot 95 weight percentaqueous ethanol mixture (200 ml.) to form a phosphine solution. Rhodiumtrichloride (3 g.) is dissolved in a hot 95 weight percent aqueousethanol mixture (200 ml.) and this solution added to the phosphinesolution. Upon cooling, an orange precipitate (10.8 g.; M.P. ca. 270 C.)falls out. This precipitate is dried in air, and is termed Catalyst A.Catalyst A is reported by B. W. Malerbi, Plat Metals Rev., 9, 47-50(1965) to be 1,2,3 tris(triphenylphosphine)trichlororhodium, while J. A.Osborn, F. H. Jardine, J. F. Young and G. Wilkenson, J. Chem. Soc. (A),1711 (1966), report these conditions to give tris(triphenylphosphine)chlororhodium. The melting point of Catalyst Asuggests that it is mainly the former with smaller amounts of thelatter.

EXAMPLE 2 This example illustrates the synthesis of a rutheniumcatalyst, termed Catalyst B, useful in the present invention.

The procedure described by Malerbi, supra, is followed and the [Ru Cl P)]+Cl" recovered and designated Catalyst B.

EXAMPLE 3 This example illustrates the synthesis of a cobalt catalyst,termed Catalyst C, useful in the present invention.

In a hood equipped with an exhaust fan are mixed cobalt octacarbonyl (1g.) and triphenylphosphine (1.5 g.) in benzene ml.). When reactionsubsides, the solution is used immediately and is termed Catalyst C.

EXAMPLE 4 This example illustrates the synthesis of additional catalystsuseful in the present invention.

Referring to Table "I, the catalysts having the designations in column 1are produced by reacting the rhodium halide of column 2 with the GroupV-A compound of column 3 in a manner analogous to that of Example 1.

TABLE I Compound of Group V-A Element (formula) cHshSb EXAMPLE 5 Thisexample illustrates the synthesis of Schiifs bases according to thepresent invention.

Into a 300 ml. magnetically stirred autoclave are placed the ethylesters of selectively hydrogenated tall oil (65 g.), aniline (19.5 g.),and Catalyst A (0.3 g.). The autoclave is sealed and the heater andstirrer started. The autoclave is then pressurized with carbon monoxideto 600 p.s.i.g. followed by hydrogen until the pressure increases to1200 p.s.i.g., whereupon heating is commenced. When the autoclavereaches reaction temperature (98 C.), the pressure begins to drop. Thepressure is then maintained at 1200 p.s.i. with alternative additions ofhydrogen and carbon monoxide supplied at an approximate molar ratio of2:1, until the pressure drops cease, which occurs after about one hour.The autoclave is then cooled, vented, and opened. The contents areremoved and distilled under vacuum at 12 mm. Hg absolute taking theindicated weights of Fractions I and II having the indicated boilingpoints.

Boiling Weight (g.) point 0.)

Fraction II is the product (70% yield), a yellow oil with a total aminenitrogen (TAN) value of 3.13.2% N (HClO The theoretical TAN value is3.35% N. The yellow oil also contains infra-red. absorptions at 3400cm.- (NH), 1735 cm. (COOEt), 1660 cm.- (N- CH), 1600 cm.- and 1500 cm.-(phenyl). The product of this reaction is almost exclusively the Schiffbase of ethyl formylstearate.

The selectively hydrogenated tall oil employed in this example is amixture of fatty acids Weight percent of which contain 18 carbon atomsand are mono-unsaturated. Of the unsaturation 35% is trans. The ethylester is formed by simply heating the fatty acids with ethanol in thepresence of a known esterification catalyst.

EXAMPLES 6, 7 AND 8 These examples illustrate the synthesis of aminesaccording to the present invention, employing fatty acid amines.

The procedure of Example 1 is closely repeated employing the samequantities of reactants and the same times and conditions, except thatthe ethyl ester of hydrogenated tall oil is replaced by an equimolaramount of the fatty ester of column 2 of Table II, the molar ratio ofaniline to fatty ester is changed to that of column 3, and the reactiontimes and temperatures are those shown in columns 4 and 5. The yield isrecorded in column 6.

The products in these cases are the N-phenylaminomethylated esters.Typical analysis: TAN 3.45% N, Calculated 3.47% N; IR bands at 3410 emf(NH), 1735 cm." (COOR), 1610 cm? and 1510 cm.- (phenyl). The absence ofa band at 1660 cm.- shows the absence of a Schiff base.

Elemental analysis.Calculated for C H NO (Example 6) (percent): C,77.70; H, 11.27; N, 3.36. Found (percent): C, 77.90; H, 11.68; N, 3.51.

TABLE II Molar ratio of Reaction conditions aniline to fatty ester TimeTemp. Yield Example No. Fatty ester (deslg) (unitless) (hrs) 0.)(percent) 6 Same as Example 5 1. 56:1 78

, 4. 33 122 7 d0 1. 5.1 4 71 8 Methyl oleatc 1 1. 4:1 2.75 122 Z 57radical, 6% of which were trans unsaturated.

2 72% based on recovered startmg materials.

EXAMPLE 9 This example illustrates the synthesis of amines according tothe present invention, employing a terminal olefin.

In a manner similar to that of Example 5, l-hexadecene (100 g.), aniline(60 g.), and Catalyst A (0.3 g.) are reacted in an autoclave. At 122 C.the pressure drop per unit time is found to be over 1000 p.s.i.g./min.Within minutes the reaction is substantially complete. The product fromthe autoclave is then distilled to give N-heptadecyl aniline (12.5 g.,TAN 3.90% N, calcd. 4.22% N). N,N-diheptadecyl aniline (45.5 g., TAN2.11% N, calcd. 2.46% N) remains as the pot residue which is decolorizedby percolation of a benzene solution through a column of alumina.

EXAMPLE 10 This example illustrates the synthesis of amines according tothe present invention, employing an a-olefin in the presence of ethanolas a solvent.

l-decene (111 g.), aniline (50 g.), ethanol ml.), and Catalyst A (0.3g.) are sealed in an autoclave and reacted as described in Example 4,except that the autoclave is heated to 150 C. for minutes after rapidgas absorption has ceased. The autoclave is then cooled and the contentsdistilled rapidly to give the product (115 g.). Only a very small amountof material remains in the distillation flask. The product consists ofN-undecyl aniline (TAN, calcd. 3.49% N. Found: 3.51%), boiling point 118C./0.01 mm. Hg, 34% yield and N,N-diundecyl aniline (TAN, calcd. 5.67%N. Found: 5.77% N), boiling point 193 C./0.015 mm. Hg, 66% yield.

EXAMPLE 11 This example illustrates the synthesis of amines according tothe present invention, employing a fatty nitrile as the olefin.

In a manner similar to that of Example 5, oleonitrile (84 g.), anilineg.), and Catalyst A (0.3 g.) are reacted at 121 C. in an autoclave withhydrogen and carbon monoixide. After cooling, the contents of theautoclave are distilled. The main fraction distills at 212 C./ 0.075 mm.Hg, to give about 71.5 g. (59%) of a yellow oilN-phenylaminornethylstearonitrile. (TAN, calcd. 3.6 6% N. Found: 3.77%N) The infra-red spectrum of the product has an absorption at 2250 cm.-characteristic of the nitrile group.

EXAMPLE 12 at 0.1 mm. Hg, as a pale yellow oil which is theN-phenylaminomethylstearylamine.

Analysis.-Calcd.: Aliphatic amine 3.75 N. Found: Aliphatic amine 3.72%N. calcd.: Aromatic amine 3.75% N. Found: Aromatic amine 3.72% N.

EXAMPLE 13 This example illustrates the synthesis of acids of thepresent invention from corresponding alkyl esters.

A sample of N-phenylaminomethylated methyl oleate (methylN-phenylaminomethylstearate) (41 g.) of Example 8 is mixed with diluteethanolic potassium hydroxide 14 g. KOH in 200 ml. 50% aqueous ethanol)and heated at 50 C. for 4 hours. After the solution has cleared, it isacidified with acetic acid to give an oil identified asN-phenylaminomethyl stearic acid. This oil is extracted into ether, andthe extracts are washed with Water several times. The extract is thendried (Na SO and concentrated under vacuum to give a yellow oil thatanalyzes as follows:

TAN, calcd. 3.59% N. Pound: 3.25% N. Neut. eq., calcd. 389.5 g./eq.Found: 389 g./eq.

EXAMPLE 14 This example illustrates the synthesis of amines according tothe present invention, employing a cyclic olefin.

In a manner similar to that of Example 11, 1,5-cyclooctadiene (50 ml.),aniline ml.), ethanol (50 ml.), and Catalyst A (0.3 g.) are reacted withcarbon monoxide and hydrogen. Distillation of the reaction mixture givesa mixture of products (47 g.) with an average total amine nitrogen valueof 6.0. (Theory for a 1:1 adduct, 6.50% N.)

EXAMPLE 15 This example illustrates the synthesis of amines according tothe present invention, employing a naturally occurring triglyceride asthe olefin.

Soybean oil g.), aniline (60 g., 0.65 mole), and Catalyst A (0.4 g., 410 mole) are sealed in an autoclave equipped with a stirrer. The stirreris started and carbon monoxide added until the pressure increases to 600p.s.i.g. Hydrogen is then added until the pressure further increases to1200 p.s.i.g. The reaction is run at 107 C.

for 1.5 hours and then at 125 C. for 4.5 hours while adding carbonmonoxide and hydrogen to maintain the pressure at 1200 p.s.i.g. Theautoclave is then cooled, vented, and the contents removed. The reactionmixture is steam distilled until the distillate is free of aniline. Thedistillate is then dissolved in benzene and passed over a column ofalumina (Alcoa F-20) to remove the catalyst. The resulting product isthen concentrated to a cloudy oil (103 g.) TAN 1.40% N. Thin-layerchromatography of this sample in benzene shows it to be homogeneous andfree of unreacted aniline.

EXAMPLE 16 The rest of the reaction mixture is fractionally distilled togive a lower boiling fraction (19.4 g.) of methyl oleate. The Prowlum fExam!1e 15 1s repeated except that The main fraction 76 g.) distillsfrom 206-218 07005 the soybean oil is replaced with tallow, with similarmm Hg (most at 2114120 C1005 mm A Center reSul cut is taken foranalysis.

EXAMPLE 17 Analysis.-Found (percent): C, 77.61; H, 11.42; N,

This example illustrates the synthesis of ethyl z-(N- A N iahphaficcyclohexylaminomcthyl) stearate wherein z is- 6 to 14 by The dlstlnatlonf' (S 15 shown by T analysls hydrogenation (benzene) to contain some ofthe main reaction product.

Ethyl z (N pheny1amin0methy1)swamte (117 g 028 All of the high boilingfraction gives only a single spot mole) of Example 7, ethanol (75 ml.)and 5% Rh/C by TLC (benzene): catalyst (4 g.), available from EnglehardIndustries, are The NMR spectrum of the mam Shows P placed in a 300 ml.autoclave and the mixture is vigorous- Hons at 50345 (Severaloeflapplflg absorpnons, 1y stirred at 110 C. under a hydrogen pressureof 1400 C1'7H34), P-P- (doublet, AB 2- p.s.i.g. After 7 hours, more 5%Rh/C (4 g.) is added and H C CH N the above conditions are repeated for3 hours. 'Upon cool- 2 ing, the reaction mixture is removed from theautoclave, filtered and concentrated under vacuum. A portion of the (twoSmglets partially superimposed residue (100 g.) is then vacuum-distilledto give a water- H and s) and 6- .4 ppm. (complex white mobile oil 78g.), boiling point 221-223 c./0.4 2 mumplet: CHHQ- mm. Hg. The infra-redspectrum of this oil is free of aromatic absorptions at 1500 cm. and1600 cm. EXAMPLES Analysis.-Calcd. for C H NO (percent): TAN (aliphatic3.30); TAN (aromatic 0.0); tertiary amine nitrogen 0.0; primary aminenitrogen 0.0. Found (per- 25 cent): TAN (aliphatic 3.2); TAN (aromatic0.1); tertiary amine nitrogen 0.25; primary amine nitrogen Theseexamples further illustrate the present invention employing certainfatty olefinic compounds reacted under varying conditions.

The procedure of Example 18 is followed, employing the same times,conditions and reactants, except that the 0.2l. methyl oleate isreplaced :by an equimolar amount of the EXAMPLE 18 olefinic compound ofcolumn 2, Table III, the molar ratio of aniline to olefinic compound isthat of column 3, the This example illustrates the synthesis of methylz-(N- reaction conditions are those of columns 4 and 5, and thephenylaminomethyl)stearate wherein z is an integer of type and amount ofproducts are shown in columns 6 from 6 to 14 inclusive. and 7.

TABLE III Molar ratio Reaction conditions Products of aniline Olefin toolefin Time Temp. Yield Example No. (design) (unitless) (hrs) C. Type(design.) (percent) 19 1.5;1 }Etz-(N-PAM)stearate 7s 20 1. 5:1}Etz-(N-PAM)stearate 77 21 13 2. 5: 1 3. 0 150 Aniline plus N-PAMproduct undistillable redisue 23 22 2. 5:1 2. 0 125 Et 2-(N-PAM)stearate23 l 3. 4:1 2. 0 }Aniline of monoaldchyde-uncertain structure TAN 3.08%18 24 Oleylnitrile 1. 7:1 2. 5 122 Mixture of anil. and N-PAMstearylnitrile 67 25 Tallow 4. 0:1 }So1.id triglyceride TAN 0.9%

1 Ethanol used as a solvent.

2 The ethyl ester of the selectively hydrogenated tall oil fatty acidsof Example 5.

8 Catalyst A replaced by an equal weight of Catalyst 0.

4 Et is ethyl, z is 7 to 13, PAM is phenylaminornethyl.

5 Ethyl linoleate is prepared by esterifieation of ethyl alcohol wlth asample of linoleic acid supplied by the U.S. Department of AgricultureNorthern Regional Laboratory.

Into an autoclave equipped with a stirrer are placed EXAMPLE 26 methyloleate (98.5 g., 0.33 mole), aniline (34 g., 0.37

mole), and Catalyst A (0.3 g., 3X10 moles). The auto- This exampleillustrates the hydrogenation of nitriles clave is then sealed and thestirrer started before carbon f th present invention to producez-(N-phenylaminomonoxide 0-750 p.s.i.g.) and hydrogen 7504500 00methyh-stearylaminep.s.i.g.) are added. The reaction mixture is thenheated Th oleylnitrile derivative containing both the Schitr at C. forminutes, during which time additional ase and theN-phenylaminomethylstearylnitrile (71 go hydrogen and carbon monoxideare added. The autoclave H1016) of Example 24 is miXed t a 5- N lut n isthen cooled, vented, and opened. The contents are reof ammonia inethanol and Raney nickel moved and the autoclave rinsed with benzenewhich is 65 p) in an aUtOClaVe- The ti n mixture is heated to then.added to the water-containing reaction mixture and 38 C- for 5 hoursunder a hydrogen pressure of 1000 concentrated on a rotary evaporator.Upon standing over- P- The autoclave is then emptied and the Contentsnight, part f h crude reaction mixture (3 g) crystalfiltered,concentrated and distilled under vacuum to give lizes, is removed byfiltration and recrystallized twice from a main fraction 0 g Pointacetone to give shiny white plates, melting point 745- 70 mm Hg, as anearly Colorless 01L Analysls y TLC 75'50 C. zene-ether-ammoniumhydroxide, 5014921) shOWs that the Analysis.-Calcd. for C H NO(percent): C, 77.36; main fraction is homogeneous- H, 11.25; N, 3.47.TAN (aromatic 3.47); TAN (aliphatic Analyse-Aided, for aa ae a (p TAN0.0). Found (percent): C, 77.23; H, 11.26; N, 3.53. TAN phatic 3.74);TAN (aromatic 3.74). Found (percent): (aromatic 3.45); TAN (aliphatic0.0). 75 TAN (aliphatic 3.72); TAN (aromatic 3.72).

11 EXAMPLE 27 This example illustrates the synthesis of an anilaccording to the present invention.

Into an autoclave are charged ethyl octadecenoate (130 g., 0.42 mole),aniline (76.5 g., 0.82 mole), and Catalyst A (0.3 g., 3 10- mole). Theautoclave is then sealed, the stirrer started and carbon monoxide (-700p.s.i.g.) and then hydrogen (700-1400 p.s.i.g.) added. The autoclave isheated to 103 C. within minutes and reaction, as indicated by a pressuredrop, occurs rapidly, exhibiting a pressure drop per unit time of about100 p.s.i.g./min. After the reaction temperature has been maintained for2 hours, the autoclave is cooled, vented, emptied, and the reactionmixture distilled. After the excess aniline is removed, the temperaturequickly rises to 200 C./0.5 mm. Hg and the product, a yellow oil (141g., 82% of theory), is collected in the range of 200-204" C., most at228 C. at 0.5 mm. Hg. The distillation residue (17 g.) is found by TLC(benzene) to be similar to the distillate. TLC of this reaction productshows a spot due to aniline and another spot indicating another aromaticamine upon spraying with developer (ceric ammonium sulfatesulfuricacid). Heating of the chromatogram shows an additional spot. That thisanil probably contained a small amount of the N-phenylaminomethylatedproduct is indicated by the TLC behavior and by the infra-red spectrumwhich had absorptions at 3400 cm? (N-H), 1735 cm." (COOEt), 1660 cm.-(-N=CH-), 1600 cm. and 1500 cm. (phenyl).

Anwlysis.-TAN (aromatic), calcd. 3.35%. N.W.

417.5 g./mole. TAN, found 3.16%. M.W. 406 g./mole.

Steam distillation of this material and subsequent vacuum distillationgives a main fraction boiling point 158 C./ 0.02 mm. Hg that is free ofaniline. This sample forms a 2,4-dinitrophenylhydrazone that isrecrystallized from cold ethanol, melting point -46" C.

EXAMPLE 28 This example illustrates the process of the present inventionemploying a ruthenium catalyst.

Into an autoclave is charged l-hexadecene (100 ml.), aniline ml.), andCatalyst B (0.3 g.). The autoclave is sealed and pressurized and thehydrogen and carbon monoxide added. After 3 hours at 140 C., thereaction is stopped and the reaction mixture distilled to give N-heptadecylaniline (containing some Schiff base), TAN 3.90 in 8% yield,and N,N-diheptadecylaniline, TAN 2.11 in 46% yield.

EXAMPLE 29 This example illustrates the process of the present inventionemploying aromatic amines other than aniline.

The process of Example 19 is repeated employing the same times,conditions, temperatures, and reactants, except that the aniline isreplaced respectively by an equimolar amount of p-anisidine,2,6-xylidine, and then 1- amino-naphthalene, with similar results.

Although the invention has been described in considerable detail withreference to certain preferred embodiments thereof, it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described above and as defined inthe appended claims.

What is claimed is:

1. A process for preparing N-alkylated aromatic amines which comprisesreacting at a temperature of from about 125 200 C. and at a pressure offrom about 200- 2000 p.s.i.g., a reaction mixture of carbon monoxide,hydrogen, an aromatic amine having the formula 1 2 wherein R is halogen,a lower alkyl or lower alkoxy, and x is an integer from 0-3, inclusive,and an olefin having the formula CnHmR wherein n is an integer from 2 to27 inclusive, m equals 2n, 2n-1 or 2n2, and R is hydrogen, hydroxy,nitrile or where p is an integer from 1 to 27 inclusive, in the presenceof a catalyst consisting of a complex of a salt selected from the groupconsisting of a rhodium halide, a ruthenium halide and a cobalt carbonylwith a complexing agent selected from the group consisting oftrihydrocarbyl phosphine, trihydrocarbyl arsine and trihydrocarbylstibine in which said hydrocarbyl substituent is a lower alkyl or phenylradical, and wherein said reaction mixture the molar ratio of hydrogento carbon monoxide is at least about 2:1 respectively, and the molarratio of the aromatic amine to the olefin is from about 1:1 to 4:1,respectively.

2. The process of claim 1 wherein the salt is a rhodium 0r rutheniumhalide.

3. The process of claim 2 wherein the salt is rhodium trichloride.

4. The process of claim 3 wherein the complexing agent has the formula:

wherein R is phenyl or lower alkyl and X is phosphorus, arsenic orantimony.

5. The process of claim 3 wherein the complexing agent has the formula:

wherein R is phenyl or lower alkyl and X is phosphorous.

6. The process of claim 5 wherein the catalyst is rhodium trichloridetris(triphenylphosphine).

7. The process of claim 6 wherein the aromatic amine is aniline.

8. The process of claim 7 wherein the olefinic compound is selected fromthe group consisting of esters of ethylenically unsaturated fatty acidsand ethylenically unsaturated fatty nitriles.

References Cited UNITED STATES PATENTS 2,750,417 6/ 1956 Closson et a1.260-577 2,859,251 11/1958 Linn 260-577 3,217,040 11/1965 Schmerling260-577 3,321,514 5/1967 Eisenmann 260-404 3,444,203 7/1965 Kurtz260-577 FOREIGN PATENTS 1,459,643 10/1966 France 260-453 OTHERREFERENCES Fieser et al.: Organic Chem. (1956), Rheinhold Pub. Co.,N.Y., 3rd. ed., pp. 197, 211 and 212.

Wilkinson: Hydrogenation, hydroformylation and Carbonylation withHalogen Complexes, (1966), CA67, No. .53652d (1967).

LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl.X.R.

8-1155; 44-66, 71, 72, DIG. 1; 117-1395; 260-2R, 77.5CH, 78R, 465E,471A, 518, 553, 558, 561, 566, 567.6, 576, 577, 599, 6188, 618F, 618H;424-304, 309, 316, 317, 318, 326, 329

